Pressure and temperature dependence of the gas-phase reaction of silylene with dimethyl ether

Alexander, Ula N.; King, Keith D.; Lawrance, Warren D.

doi:10.1039/b100068n

Cited by 24 publications

(66 citation statements)

References 26 publications

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“…16,17 It is expected that the GeH 2 reactions studied here will show similar pressure dependence to that exhibited for SiH 2 . Consequently, the data are expected to provide rate constants far from the high-pressure limiting values.…”

Section: Resultsmentioning

confidence: 95%

“…16,17 The experiments reported here are up to 200 Torr in SF 6 . The limit of 200 Torr arises because the signal levels for the GeH 2 system decrease with increasing pressure.…”

Section: Resultsmentioning

confidence: 99%

“…The pressure dependence is analogous to that observed for SiH 2 reactions with the same species. 16,17 While the data are not of sufficient quality to establish a pressure dependence in the case of D 2 O, it is likely, based on the reaction of SiH 2 with Fig. 1 Typical decay trace for GeH 2 (25 mTorr of PhGeH 3 precursor) reacting with 0.5 Torr CD 3 OD at 150 Torr total pressure (SF 6 bath gas) and 295 K. The points are experimental data while the solid line is the biexponential fit to these data.…”

Section: Discussionmentioning

confidence: 99%

“…The purpose of this paper is to report the first such study, focussing on the reactions of GeH 2 with CH 3 OCH 3 (Me 2 O), CH 3 OH (MeOH), CD 3 OD and D 2 O. We have recently completed and reported on an extensive study of the reaction of SiH 2 with these reactants 16,17 and have previously published rate constants for singlet methylene, 2 CH 2 , reacting with such species. 18 Consequently, there is the opportunity for a comparison between the three group XIV analogues reacting with n-donor bases.…”

Section: Introductionmentioning

confidence: 99%

“…This effect has also been seen in our previous kinetic studies of singlet CH 2 and SiH 2 . [16][17][18][21][22][23][24][25][26][27][28] We have shown previously that the rate constants are independent of photolysis wavelength, indicating that vibrational relaxation is not an issue in this system. 9 The rate constants reported here were obtained with total cell pressures in the range 10-200 Torr.…”

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confidence: 99%

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Rate constants for the gas-phase reactions of germylene with CH3OCH3, CH3OH, CD3OD and D2O at ambient temperature

Alexander

King

Lawrance

2003

Phys. Chem. Chem. Phys.

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Gas-phase rate constants for the reactions of germylene, GeH 2 , with dimethylether (CH 3 OCH 3 ), methanol (CH 3 OH), deuterated methanol (CD 3 OD), and deuterated water (D 2 O), have been determined at ambient temperature (295 K) and total pressures over the range 10-200 Torr of the bath gas SF 6 . The second-order rate constants are pressure dependent up to the maximum pressures investigated. The behaviour of GeH 2 with these reactants is very similar to the behaviour observed for silylene, SiH 2 . Over the same pressure range the GeH 2 reaction rate constants are smaller than those observed for SiH 2 .

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Section: Resultsmentioning

confidence: 95%

“…16,17 The experiments reported here are up to 200 Torr in SF 6 . The limit of 200 Torr arises because the signal levels for the GeH 2 system decrease with increasing pressure.…”

Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

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Rate constants for the gas-phase reactions of germylene with CH3OCH3, CH3OH, CD3OD and D2O at ambient temperature

Alexander

King

Lawrance

2003

Phys. Chem. Chem. Phys.

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Theoretical Study on the Reactivities of Stannylene and Plumbylene and the Origin of their Activation Barriers

2004

Chemistry A European J

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The potential energy surfaces corresponding to the reactions of heavy carbenes with various molecules were investigated by employing computations at the B3LYP and CCSD(T) levels of theory. To understand the origin of barrier heights and reactivities, the model system (CH3)2X+Y (X=C, Si, Ge, Sn, and Pb; Y=CH4, SiH4, GeH4, CH3OH, C2H6, C2H4, and C2H2) was chosen for the present study. All reactions involve initial formation of a precursor complex, followed by a high-energy transition state, and then a final product. My theoretical investigations suggest that the heavier the X center, the larger the activation barrier, and the less exothermic (or the more endothermic) the chemical reaction. In particular, the computational results show that (CH3)2Sn does not insert readily into C-H, Si-H, C-H, Ge-H, or C-C bonds. It is also unreactive towards C=C bonds, but is reactive towards C identical with C and O-H bonds. My theoretical findings are in good agreement with experimental observations. Furthermore, a configuration mixing model based on the work of Pross and Shaik is used to rationalize the computational results. It is demonstrated that the singlet-triplet splitting of a heavy carbene (CH3)2X plays a decisive role in determining its chemical reactivity. The results obtained allow a number of predictions to be made.

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Gas phase kinetic and theoretical studies of reactions of germylenes and dimethylstannylene

et al. 2005

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The results of time resolved gas phase studies of labile germylenes (GeH 2 and GeMe 2 ) and dimethylstannylene (SnMe 2 ) reactions reported to date are considered together with data of quantum chemical investigations of the potential energy surfaces of these systems. Reaction mechanisms are discussed. A comparison of reactivity in the series of carbene analogs, ER 2 (E = Si, Ge, Sn, R = H, Me), is made.

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Pressure and temperature dependence of the gas-phase reaction of silylene with dimethyl ether

Cited by 24 publications

References 26 publications

Rate constants for the gas-phase reactions of germylene with CH3OCH3, CH3OH, CD3OD and D2O at ambient temperature

Rate constants for the gas-phase reactions of germylene with CH3OCH3, CH3OH, CD3OD and D2O at ambient temperature

Theoretical Study on the Reactivities of Stannylene and Plumbylene and the Origin of their Activation Barriers

Gas phase kinetic and theoretical studies of reactions of germylenes and dimethylstannylene

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